3,3-dimethyl-2-norbornane propionic acid

ABSTRACT

A process of preparing certain alpha substituted carboxylic acid anhydrides by reaction of a compound having ethylenic unsaturation (preferably at a terminal position) and an anhydride of a C2-C18 carboxylic acid having an available alpha hydrogen such reaction being carried out in the presence of hydrogen peroxide as the free radical iniator. The products produced by the process are easily esterified to produce esters suitable as perfume additives or flavor additives.

United States Patent Kuder Sept. 5, 1972 [54] 3,S-DIMETHYL-Z-NORBORNANEOTHER PUBLICATIONS PROPIONIC ACID Allen et al., J. Chem. Soc. 1965,1918. [72] Inventor: Robert C. Kuder, Excelsior, Minn. [73] Assignee:General Mills Inc" Prirnary ExaminerLo rraine A. Weinberger AsszstantExammer-Robert Geistl Filed: March 1969 AttorneyAnthony A. Juettner,William C. Babcock 21 I APPL 07 075 and Jerome J. Jenko Related us.Application Data 57 ABSTRACT Continuation-impart 0f 570,711, g A processof preparing certain alpha substituted car- 1966, abandonedv boxylicacid anhydrides by reaction of a compound having ethylenic unsaturation(preferably at a terminal [52] US. Cl. ..260/5l4 B position) and ananhydride of a C e carboxylic acid [51] [13L Cl ..C07C 61/12 having anavaiIabIe alpha hydrogen h reaction [58] Field ofSearch ..260/546, 514,468 being carried out in the presence of hydrogen perm ide as the freeradical iniator. The products produced [56] References cued by theprocess are easily esterified to produce esters FOREIGN PATENTS OR T O Ssuitable as perfume additives or flavor additives.

1 Claim, No Drawings 3 ,3-DlMETHYL-2-NORBORNAN E PROPIONIC ACID Thisapplication is a continuation-in-part of my copending application, U. S.Ser. No. 570,711, filed Aug. 8, 1966, now abandoned.

The instant invention relates to the preparation of certainalpha-substituted carboxylic acid compounds, and more particularly, to aprocess of combining certain carboxylic acid anhydride reactants withcertain ethylenically unsaturated reactants to effect alpha-substitutionin such anhydride reactants.

The unsaturated reactant used in the practice of the invention containsan ethylenically unsaturated group through which one might expect toobtain olefinic addition polymerization in the presence of a typicalpolymerization catalyst, i.e., hydrogen peroxide, which is a uniquecatalyst for use herein. Also, the carboxylic acid reactant used hereinis an organic acid anhydride which one might expect to function as apolymerization accelerator in combination with such hydrogen peroxidecatalyst and/or as a co-reactant therewith, e.g., to form acorresponding organic peroxide or hydroperoxide.

In contrast, the ethylenically unsaturated reactant (x) and the organiccarboxylic acid reactant (a) hereof, in the presence of such apolymerization catalyst (b), hydrogen peroxide, are believed in thepractice of the invention to undergo primarily a reaction according tothe following oversimplified Equation (A):

wherein it will be seen that anhydride reactant (a) is represented by anacyl group and so is the acid anhydride product (P). Reaction product(P) is substantially a 1:1 adduct of the specific unsaturated reactant(x) and the carboxylic acid anhydride (a), based on the acyl or acetylequivalent thereof, vis-a-vis the unsaturation at the methylene group:=Cl-I in (x).

A conventional textbook type of olefin-carboxylic acid reaction to forman ester is described in Groggins, UNIT PROCESSES IN ORGANIC SYNTHESIS,Fourth Edition, 1952, McGraw-Hill (pages 627 and 639) wherein Grogginsrefers to Equation (B) below as representative of the reaction:

CH2 T Apparently the catalyst sulfuric acid commonly used to effect theunion according to Groggins (p. 627) leaves something to be desired, andhe suggests that it is desirable to get away from the polymerizingeffects of sulfuric acid. Groggins further points out that the reactionof Equation (B) does not go well with ethylene but does with many higheralkenes, particularly with some terpenes (page 627); and later (page639) Groggins explains in greater detail how mild esterificationconditions with terpenes, according to his Equation (B), are to beemployed to minimize undesirable polymerization and/or isomerization. Itwill be seen that certain terpenes happen to be capable of advantageoususe in the present invention; but for use according to previous Equation(A), and not in the esterification process B) of Groggins. Moreover, itwill be found herein that typical polymerization catalysts (i.e., peroxycatalysts) are very effective in catalyzing reaction (A) even thoughpolymerization of the olefinic reactant (x) is substantially avoided inthe practice of the invention.

Prior to and since Groggins, a number of workers have laid claim to avariety of discoveries relative to the use of ethylene in reactionsgeneralized by Equation (C) below:

w .cwcraco- 1' .aswaaryicqrrqwherein allegedly significant and differentvalues are given for n ranging from 1 to very high numbers. Each suchworker has urged some particular set of reaction conditions, reactantsand/or factors allegedly unique for his purpose (e.g., Hanford et al.,U. S. Pat. No. 2,402,137 in 1946; Roland et al., U. S. Pat. No.2,433,015 in 1947; and Banes U. S. Pat. No. 2,5 85,723). Banes alonerecites H 0 but shows only the use of organic peroxy catalysts and onlyacid not anhydride reactants.

Some more recent workers have mentioned the use of higher alkenes thanethylene, e.g., Moote U. S. Pat. No. 2,823,216 in 1958, who explainsthat in his reaction using C, to C alkenes he must use at least a Ccarboxylic acid because acetic is not satisfactory for his reaction.This latter difficulty is apparently overcome by Hey et al., in BelgianPatent No. 621,365, French Pat. No. 1,330,454 and British Pat. No.960,894 (1964) who claim to use acetic acid, acetic anhydride, ethylacetate and a variety of other CH CO-- compounds for reaction withalkenes, specifically showing octene-l, butene-l, decene-l andheptene-l, in the presence of various catalysts including organicperoxides in the examples.

The foregoing Hey et al. disclosures are not completely identicalorconsistent, except perhaps in the specific descriptions of the examplestherein. Thus, in the Hey et a1. French and Belgian patents, the olefinsare described in general terms including X C CX wherein each X may bealkyl, hydrogen, etc., whereas the British patent would appear to beexpressly limited to X C CH type olefins. On the other hand, only theBritish patent mentions cyclohexene (page 1, line 50) even though noexample for the use thereof is shown, and this particular olefinic typeis otherwise clearly excluded from the scope of the British patentdisclosure and claims.

In a late 1965 publication by Hey (as co-author with Allen and Cadogen,J. Chem. Soc. 1965, 1918-32) reference is made to various theoreticalconsiderations involved relative to specific reactions comparable tothose shown in the aforesaid British patent; but again withoutdescribing a specific experiment by the authors using cyclohexene.Instead, on pages 1928-9, the authors confess to an apparent anomaly ina report of Nagai et al. (J. Chem. Soc. Japan) indicating that thebenzoyl peroxide addition of chloracetic acid to cyclohexene involvesabstraction of chlorine; but the observation of the Hey et al. group ismade relative to their own work with the ester, ethyl chloroacetate, andwithout representation as to work actually done by them in connectionwith any cycloolefin (including cyclohexene).

In such 1965 publication (pages 1928-29), thus, Hey et al. observe thatthe following Equation (D) is allegedly known:

They then note that Nagai et al have alleged that the benzoylperoxide-initiated addition of chloroacetic acid to cyclohexene involvesabstraction of chlorine presumably according to Equation F):

/H, /og,

Cl CH2 CH I CH2 CHCl H HCCOOI-I --s 052 /CH Ill C52 CHCHzCOOH CH2 H2all).

wherein the ethylenic unsaturation between the intracyclic Us ispresumably satisfied in part by the alpha- Cl. Hey et al. do notdescribe a different experimental result; but do point out that priorart suggestions and their own work relative to cyclohexanone-olefin andcyclohexylacetate-olefin additions appear to reveal certainpeculiarities of intracyclic groups in these cycloaliphatic ketonesand/or esters when used as reactants with olefins. Hey et a1 do not,however, describe any work of their own relative to the use ofcycloaliphatic olefins with carboxylic acid reactants( or the use of H 0In contrast, it is a primary object of the instant invention to providea novel process for preparing certain alpha-substituted carboxylic acidanhydrides, accord- .ing to previous Equation (A), by reaction of x) acompoundhaving ethylenic unsaturation (preferably at a terminal carbonposition) and (a) an anhydride of a C to C carboxylic acid having anavailable alphahydrogen atom, such reaction being carried out under freeradical forming conditions (specifically via the presence of aforesaidunique H 0 initiator) substantially in liquid state reaction mix and ina substantial molar excess of a) sufficient to effect primarily reac'tion of one equivalent of (x) with each carboxylic acid equivalent ofsuch anhydride (a). It is a further object to provide the anhydrideproduct of such process.

Other and further objects, features and advantages of the presentinvention will be apparent from the following disclosure and examples.

In appreciating fully the inventive concept here involved, it isimportant to understand that in the case of the reaction of reactant (a)with various different unsaturated reactants (x), in the presence ofperoxide initiators or promoters (b), these various initiators and/orpromoters (x) do have varying abilities relative to achieving goodyields in the desired reactionbetween reactants a) and (x). Thus it willbe seen in the disclosure immediately following that, in the case ofcertain terpenes (x) and in the case of some of the more reactive andlower molecular weight anhydrides (a), e.g., formed from C C acylgroups, it does appear that the specific organic peroxide,tertiary-butyl peroxide (b seems to produce a better yield or a betterconver sion of the terpene than the much less expensive hydrogenperoxide (1),), even in certain instances involving the use of a greaterproportion of the hydrogen peroxide. Of course, even if twice the molarproportion of hydrogen peroxide is used in a given reaction the cost ofthe hydrogen peroxide used is much less than the cost of the aforesaidorganic peroxide (b,). For a comparison, 22 pounds of the organicperoxide (b,) has a cost of approximately $38.50 at the present time;whereas twice the molar proportion of hydrogen peroxide, i.e., 10 poundshas a cost of approximately $5.00.- Comparing subsequent Examples 1 and3, it will be seen that the difference in the amount of campheneconverted is about 30 grams, using pounds it would be 30 pounds at 14per pound or about $4.20 less camphene actually converted into theproduct. Of course, all of such camphene that is not converted is notall lost; and this calculation could be reversed to incorporate acomparable cost difference of about $4.00 if computed on .the basis ofthe actual cost of ingredients actually converted into the finalproduct. In any case, it is apparent that the principal item of cost isin the promoter and the mere fact that it appears that the yield isapproximately 30 percent lower using hydrogen peroxide in Example 3 doesnot subtract from the fact that the product actually obtained in Example1 happens to cost approximately 2 to 3 times more per pound. Thisdifference is sufficient to take into consideration the expectedfluctuations in the price per pound of the various ingredients over asubstantial period of time in the future. Of course, if one were torequire elaborate and expensive refinement and purification in the caseof, for example, the camphene material in order to obtain an expensivelypurified camphene for use in the instant reaction, then it isconceivable that the somewhat improved yield obtained by the use of theorganic agent (b would be a much more significant factor economically.

The concept of the invention contemplates, in general, using variousunsaturated reactants x) which are available at reasonable prices and,further, using the inorganic promoter, hydrogen peroxide (b to obtain anunexpectedly and remarkably good yield so as to achieve whollyunexpected economic advantages in the practice of the instant invention.In the specific cases just mentioned relating to camphene, the loweryield obtained with hydrogen peroxide is significant and noticeablenumerically, but it does not subtract from the economic advantages.Subsequently herein it will be demonstrated that practically the sameyield is actually obtained using hydrogen peroxide, as is obtained usingthe organic peroxides, i.e., particularly with a number of thealpha-olefinic chain compounds; and in such situations the equally goodyieldas well as the economic advantages will demonstrate even moreconclusively the remarkable character of hydrogen peroxide as a promoterin this specific reaction system.

The cyclo aliphatic anhydrides of the instant invention constitute a newclass of compounds useful in a variety of chemical syntheses. Theseanhydrides are very reactive and may be converted by known methods tothe corresponding acids, salts, esters, nitriles, amides, chlorides, orother derivatives. These anhydrides are especially useful when convertedto'esters as disclosed in my copending application, U. S. Ser. No.570,772 filed Aug. 8, 1966. These esters are useful in perfumes.

These anhydrides may be described generally by the definition: Acycloaliphatic organic acid anhydride formed of (x) at least onecycloaliphatic C to C hydrocarbon group wherein the only available bondsare provided in-the form of single bonds on otherwise saturatedexocyclic C atoms and (a) at least one C to C acyl group each having atleast one carbonyl group providing one bond for direct connection to theanhydride oxide atom and a second bond for direct connection to an alphaC atom which, in turn, provides a single bond for direct connection toone of said exocyclic group (a) C atoms; such that the groups (a) and(x) are bonded together only vis a-vis said exocyclic group (x) C atomsand said group (a) alpha C atoms; theonly atoms other than H and C atomsin each such acyl group (a being in the aforesaid carbonyl groups.

Also, the characteristic relative structural relationship of alpha, betaand gamma carbon atoms may be used in a more specific definition,wherein the new compound of the invention is defined as a cycloaliphaticorganic acid anhydride characterized by the structure:

wherein C1, C and Cu represent, respectively, gamma, beta and alphacarbon atoms and represents an acyl carbonyl group having a bondavailable to satisfy the anhydride oxide equivalent: (0)%; saidanhydride consisting essentially of (x) from one to two cycloaliphatic Cto C hydrocarbon groups each having at least one cyclic nucleuscontaining at least four nuclear Us and each such (1:) group havingavailable bonds only in the form of single bonds on each of from. one tothree exocyclic saturated C atoms each of which is in turn connecteddirectly to a C the aforesaid group (1:) available bonds being satisfiedby direct connection between each said C atom and an equal numbergf Cuatoms in (a) from one to three C;

- to C acyl gioups each having from one to two available bonds only inthe form of single bonds each attached to C atoms each of which isattached to an acyl carbonyl-oxide group:

of said structure, such carbonyl-oxide groups containing the only atomsin such acyl groups (a) other than H and C; and in the correspondingdefinitions for the derivatives thereof such as acids, salts, esters,ketones, nitriles, etc. the

group in the above definition is replaced by (lT-OH, -CN, fIJOM(Cation),

alkyl or alkenyl, glycol, polyglycol, carbotol, poly-OH (glycerol,pentaerythritol, sorbitol, etc.) as it appears above in either ester orketone.

The adducts of this invention are prepared by adding the olefin and asmall amount of a peroxide initiator gradually, over a period of severalhours, to a large excess of boiling acetic anhydride(reaction-temperature is usually l35-140 C.). If the olefin is a solidsuch as camphene), it may be predissolved in part of the aceticanhydride before adding it to the reaction-mixture. It will beappreciated that this procedure provides for a very substantial molarexcess of acetic anhydride at all times, beginning with the firstincremental additions of the olefin and peroxy catalyst, and continuingto maintain the substantial molar excess of the acetic anhydride withsubsequent incremental additions of the olefin and the catalyst. Thefollowing examples show adducts of about 2:1 in molar ratio of (a) to.(x) [i.e., l acyl (a) equivalent to each I l o=c v (x) equivalent]; butthe reaction mix should have an (a):(x) equivalent ratio within apractical range of about 10:1 to 1,000:1 (i.e., molar range of 5:1 to500:1). Preferably, the (a):(x) equivalent ratio of at least about 25:1[Ex. 2], or better about 50:1 [Ex. 3] to about :1 is preferred as theminimum. The maximum (a):(x) equivalent ratios of about 500:1 to

l000:l are determined essentially by practical considerations of plantcapacity, etc.; and all such ratios are on an overall basis, in view ofincremental additions of (x) and (b) to (a) which no doubt maintainstill higher ratios at the immediate reaction scene. The

specific adducts, olefin anhydrides, can be prepared as disclosed in mycopending application, U. S. Ser. No. 570,736, filed Aug. 8, 1966.

The primary product of Examples l-3 is probably a mixed anhydride, whichdisproportionates during distillation of the excess acetic anhydride togive the symmetrical cycloaliphatic carboxylic anhydride and aceticanhydride as indicated in Equation (A below:

CzCHz (cmcono CHOI-IzCHzCQQCOCH: l A

It is also possible that some telomerization should take place, givinghigher molecular weight materials of the type or the corresponding mixedanhydride.

According to the process of this invention, however, very little telomeris formed and the major product is the symmetrical 1:1 adduct (i.e., theadduct with n l).

The nature of the product can be elucidated by determining itssaponification number (S.N.), from which can be calculated the ratio ofacetic anhydride to olefin combined in the product; and by esterifyingthe product and separating the ester of the 1:1 adduct by d' t'llati 11hr v 0 or c qmatqgraphy of Aczo 1e identify the reactive ethylenicunsaturatlon; and it will (CH CO) O, combined in product be seen thatsuch olefimc exocyclic C becomes a satu- WM rated beta- C in theultimate product (P) wherein the C r. Maw.-. fiilQQm N r v. 7 positionsare referenced to the carbonyl group (C Wto 02 combined in p O). Thesecond C here shown in the olefin (x) which is X of product X alsoinvolved in the ethylenic unsaturation is intracyclie 56,100 in camphene(x and it becomes a saturated gamma-C *Ineludcs also any small amount ofunstripped free A020. the P q (P It Is behaved th at reactlon of theinvention 18 predicated on the availability of the alpha- Mols 0f l ficombined in product: 20 H (under the free radical promoting conditionshere in- Wt. of product Wt. of A0 0 in product volved) on the alpha-C ofthe carboxylic acid reactant (a), which is preferably the anhydride ofrelatively of olefin lower molecular weight C to C alkanoic acids. SuchMols of combined olefin anhydrides are preferred because they ordinarilypos- Conversion of olefin= sess better ability to dissolve the reactant(x) and most a. a a t W. t. M013 of charged Olefin forms of organicinitiators b), and they react The ratio, (Equiv. of combined Ac O)/(Molsof comsomewhat more readily. It should be noted that abbined olefin),will be one for the symmetrical 1:1 adstraction of the a-H of a) tothey-C of P) is herein duct, RR CHCH CH CO),O; or two for the mixed 1:]promoted by inorganic H 0 (b as well as the organic adduct, RR'CHCI-I CHCOOCOCH The presence of free radical initiator( h telomers (n 2 or more)in the product would lower In general, the anhydride reactants (a) maybe the values of this ratio. formed of C to C alkanoic acids, e.g.,acids contain- The reaction of Examples 1 through 3, is represented ing2 to 18 C atoms such as acetic (a propionic (a conveniently by thepreviously mentioned simplified 3 butyric (a isobutyric (a pentanoic (acaproic Equation (A), or the specific Equations (A and (A 5 (a heptanoic(a caprylic (a nonanoic (a below: capric (a undecanoic (a lauric ordodecanoic (A1) (X1) (211) (P!) CH2 (HZ 0 l\ a CH 0:0112 OHGC CH2cream-011200 2 Hz 1 +v \O 1 CH2 CH2 o on3 omoi CH2 0-0113 CIIJ \O CH2 0112 CIIZ 01-12 04 0 fi-om-omo 0 I 1H2 CH2 CCH3 CH3 C 2 (A2) (X1) (m)(P1) CH3 l In the case of the olefin a having the exocyclic methylenegroup CH the carbon atom thereof (which may be referred to as thealpha-carbon of an alpha-olefin) indicates the exocyclic carbonposition, which is involved in or at which position one may wherein (b)is a (peroxy) compound often referred to (a tridecanoic (a myristic a pntadecanoic as a polymerization catalyst for (olefinic) additionpolymerization, but is more accurately referred to herein as aninitiator or promoter of free radical forrna-' tion. In fact, theinstant free radical formation is believed to involve the alpha-hydrogenon the acetyl group, in accordance with a reaction mechanism (M) whichmight be represented quite simply as follows:

(a palmitic (a heptadecanoic (a stearic (a acids, etc.; and preferablyacids containing no ethylenic and/or acetylenic unsaturation and/orgroups other than the principal carbonyl group) which may tend tointerfere with the reaction (e.g., hydroxy, etc.). The group attached tothe (acid) carbonyl group may be branched, e.g., diethyl acetic (adioctyl acetic (a acids, etc., or straight chain hydrocarbon, withcyclic hydrocarbon groups, e.g., methylcyclohexyl, cyclohexylmethylphenyl acetic or propionic (a acids, etc. Also, one may use mixedanhydrides of the foregoing acids (a through (a and anhydrides ofpolycarboxylic acids, e.g., succinic (a tetrahydrophthalic (a methyl orethyl succinic (n adipic (0, sebacic (a up to C dicarboxylic acids,i.e., octadecanoic (a Although the instant reaction is preferablycarried out using only the essential reactants (x), (a) and (b) in theliquid reaction mixture, in those cases wherein higher molecular weightreactants are used, it may be and often is advantageous to employanhydrous substantially inert hydrocarbon solvents such as tolueneand/or hexane or heptane (to effect a liquid state reaction mixture) butusually also using heat and some pressure to efiectively maintainreaction temperatures within the previously indicated range (andpreferably at about 105 to 205 C.). Essentially, the

anhydride reactants (a) used must have an available alpha-H (on thealpha-carbon next to the acyl carbonyl group). Such acyl group maycontain one or more acyl carbonyl groups but must otherwise be inert inthe reaction. In a mixed acyl anhydride (a), of course, only onealphanl-I is necessary; but preferably both monoacyl groups in theanhydride have alpha-l-ls.

Suitable cyclic olefins which can be used as the reactant (x) in thepractice of this invention are as follows:

Methylene-eyclop entane (x CH:C H;

CE; =CH;

Methylene-cyclohexane (x C H CH; ([1:011, 65 /CH, CH;

Dlvinyl-cyclobutane (x5) /C Ii;

CHz=CH-CH /CHCH=CH, CH

4-vinyl-1-cyclohexene (x CH;

CH CH-CH=CH Methylenecyclopentadiene CH-C=OH (x1e) (fulvene). I

H OH W CH Benzofulvene (x11) CH (iJH (|.?-?=CH Cg /O\ /CH WW7, ,A 021.M011, 7 1,%,43t?Ein3%-cyc1ohexane /C]E\I 5 CH1 CHCH=CH CH2=CH-$HlHCH=CHz CH2 u.

One preferred group of cyclic olefinic compounds (x) is the monocyclicterpenes:

A1,8(9)-p-menthaglen5e CwHm CH-CHZ CH limo! x x.

Beta-phellandreno (xw) A1(7), (Ill-=0 0 ll 2-p-menthadlene C 11".

CH2=C /ClI(Jll C H C H 1 II 3 Sylvestrene (1m) A1 8(9) m-meuthadiene dwn- 4 C HC H--- :0 H7

CH;C CH2 CH C Hz B eta-terpinene (X14) A1 (7) C H3-C II C ll;

S-m-menthndieno CmHn.

ClIz=C C-bll L C"3'-Cl[9 Lil;

A-8(9)I:1p-menthene (X15) C II -C II; C l 1';

CH -C ll Gil-{1,

CII1C6 i A-1(7)-m-menthene (X10) C ll C I -C II; @C H 5H =C (DCII IICII1CII2 @H;

Among the terpenes, the preferred compounds are the bicyclic terpenes:

Camphene (x1) N,B,Enclrcled numbers indicate numbered carbon positions,

Alpha-fenchene (xn) CH Beta-fenchene (x11) Beta-pinene (x (Ex. 4)

Sesquiterpenes (S15E24) are also used;

X used in the invention are vinyl cycloheptane (x methylene cycloheptane(x etc.

As hereinbefore indicated, the cyclic reactant (x) has reactive ethyleneunsaturation in a semicyclic position (preferably in the form of a CHgroup attached to the ring) but such unsaturation may be between a pairof exocyclic Cs, as in the isopropenyl or vinyl groups. In eachinstance, the unsaturation preferably includes the unsubstitutedmethylene group,

CH but reaction is also obtained at somewhat lower yields in the case ofintracyclic terpene unsaturation and in the case of exocyclicunsaturation wherein both Cs have some substituents, as in the case ofA-1,4($)-pmethadiene C HC Hz C H terpinolene (X21). 4

CH3-C C CHzCHz H Santalene (X22) 3 uHu.

/ CH CH J: XCCHa l wherein X is CnHn or CH CHZCH= C-CH;

segqAuicarnpthenel (x11) h -pen any -eamp ene wherein X1 is 06H or CH H1 2C 2CH2CH2CH= CH 2 il/ Q Additional ethylenically unsaturatedreactants (x) used to advantage herein (according to the proceduresherein) include:

XXX. C C alpha-olefins; i.e., mono-olefins 1- dodecene (X and ethylene(x propylene (x butylene (x and all such C C alkene-l or alpha-alkenes(r through (x Preferably, l-octene (x 1- decene (x l-dodecene (x andl-tetradecene (x may be used alone or in admixture, exactly as describedin Examples 8-1 1, in order to obtain the corresponding decanoic,lauric, myristic and palmitic acid derivatives. Lower boiling C Calpha-olefins are reacted under pressure at substantially l-l40 C. usingthe same procedures.

XXXI. C C alkenyl (C C alkanoates, (x e.g., vinyl acetate (x allylacetate (x methallyl propionate (x vinyl butyrate (x crotyl acetate (xmay all be used in place of l-dodecene in Examples 8 and 9, preferablyusing at least a few atmospheres pressure to effectively maintain areaction (and/or reflux) temperature of l35-140 C. in otherwise exactlythe same procedure as that described in such Examples.

XXXII. In each of Examples 8-1 1 and previous paragraphs (XXX) and(XXXI), it is found that the best yields-of 1:1 adducts are obtainedusing preferably about 100 equivalents of (a) to 1 equivalent of (x)(and at least about 50:1 equivalent ratio seems particularly advisable).

XXXIV. Repeating the procedures of paragraphs (XXX) and (XXXI), andExamples 8-11, using (a (a (a and/or (a substantially under temperaturereaction conditions of reflux (or at 150 C.) each as specified herein,will result in excellent yields of 1:1 adducts. Also, the higher (a)reactants of processes herein are used with the olefins (x) of paragraph(XXX) hereof to obtain 1:1 adducts.

XXXV. C, C alkenoyl nitriles (X57), acids (x chlorides (x C to C alkylesters, (X60) are used exactly as the unsaturated compounds (X30) ofExamples 8 -10 or the esters (x using undecylenic acid (x [Ex. 12]undecenonitrile (1: methyl undecylenate (x ethyl undecylenate (x butylundecylenate (x each in 1 mol proportions to 0.3 mol of H 0 active andat substantially l35-l40 C.; but preferably using 100 to 150 molecularequivalents of reactant (a) in order to effect maximum conversion to 1:1(equiv.) adducts.

XXXVI. Additionally, thehigher alkyl alkenoates (x alkenyl alkenoates (xand/or alkenyl alkanoates (x having not more than about C groups oneither side of the ester COO- group can be used. In contrast tocomparatively readily polymerizable (x) reactants such as those ofparagraphs (XXXI) and (XXXV) hereof, the foregoing may be usedeffectively in equivalent ratios of (a) to (x) as lowas 10:1, 20:1, and25:1 with minimum telomer formation; and, likewise, with the higher andmore complex (a) reactants of paragraph (XXXIV). For example, methyllinoleic (x ethyl linolenic (x methyl oleate (x oleyl acetate (xlinolenyl propionate (x vinyl oleate (x etc., may each be used, as onemol (x) predissolved in some (a,) acetic [or propionic (a butyric (aisobutyric (a.,) or valeric (a5)] anhydride for reaction with a total of50 equivalents of (a) at reflux temperature [and using 0.3 mol H 0 (bactive], for 8 hours addition and 8 more afterwards, in order toobpredominate.

XXXVII. Additionally, cycloaliphatic [C C C C (ethylenicallyunsaturated) esters, acids,

chlorides, etc., may also be used as (x), e.g., any of the C unsaturatedterpene alcohols esterified with C to C alkanoic acids, e.g., acetic (xand any of the C unsaturated terpene carboxylic acids [and/orunsaturated adducts (P) of terpenes hereof] esterified with C, to Calkanols (x are used as the reactant (x) herein, exactly as describedfor (x) in the previous paragraph, e.g., using the ethyl ester of (P as(x for reaction with said excess acetic anhydride (a,) and/or usingabietic acid (x methyl abietate (x and other tall oil fatty acids againwith acetic anhydride (a,), all as described in Example 3 hereof, effectthe adduct formation. In this respect, it is important to note that,although the adduct reaction Equation (A) goes more easily andeffectively with alpha-olefinic groups, or at least ethylenicunsaturation at an exocyclic carbon herein, in reactant (x), and suchunsaturation at exocyclic olefinic groups tends to dominate (whenpresent), it is found that, when only intracyclic unsaturation ispresent [i.e., abietic compounds (x (x and/or intracyclicallyunsaturated terpenyl (am), (1: compounds] such intracyclic unsaturationis functional significantly for the alpha-substitution on reactant (a).Also, conjugated double bond (ethylenic) unsaturation within aliphaticchains, as in the aforesaid linoleic (x and linolenic (x derivatives isfound to be very functional in (x) reactants hereof. In fact, pluralethylenic unsaturation in aliphatic poly-olefms, whether or not someunsaturation is at an alpha-position and/or in a conjugated double bondarrangement, is found to be suitable for use herein. For example,butadiene (x contains sufficiently reactive poly-unsaturation to effectplural alpha-substitution on two equivalents of (a). This is also trueof diallyl phthalate (X82) which is an ester, not an olefin. Otherrecognized (addition polymeric) olefinic monomers such as diisobutylene(x etc., are each used in place of (x,) in Example 3 with 0.3 mol H foreach equivalent thereof to obtain good results.

Although it is generally preferable to employ, as (x), a C to C organiccompound containing no atoms other than C and H except those in suchessentially inert groups as COO, CO, O, CN, C-O-Cl groups, it will beappreciated that in esters the (C to C )--COO group is often connecteddirectly to a C to C alcoholic group or residue (and such is often thecase with ether O- and keto CO groups). Di-butenyl ether or ketonerepresent the lower molecular weight groups of these categories usablealso in the invention.

The invention hereof thus involves a process of synthesizing anorganiclinkage having the structure (PP):

wherein C,,, C and C represent, respectively, gammabeta andalpha-carbons referenced to the group in said structure, which consistsin contacting (a) substantially at least to 500 molecular equivalents ofan acyl anhydride having the structure aa):

contemporaneously with (b) substantially 0.05 to one mol, but preferably0.15 to 0.5 mol of H 0 and (x) substantially one molecular equivalent ofan ethylenically unsaturated pair of Cs having the structure xx):

in a liquid mix at substantially 75 to 205 C. under free radicalpromoting conditions initiated substantially by such H O (b) andcontinuing such heating to substantially complete decomposition of suchH 0 thereby effecting chemical combination of (aa) and (xx) wherein Cand C, of (xx) become, respectively C, and C of said structure (PP) andthe double bond of (xx) is satisfied, in part, by abstraction of thealpha-hydrogen of (aa) to the C, of (xx) which, in turn, becomes the HO,of PP) and, in part, by the free radical of C 0 (aa) that is created bysuch abstraction of the alpha-H and is satisfied by C,, of (xx)converted thereby to C in the ultimate structure (PP), said processbeing carried out in an essentially anhydrous and inert system exceptfor the reacting structures (aa) and (xx), each of which is composed ofno atoms other than H and C except those in groups selected from Theproducts of the invention are the anhydrides of the process and/or theirpolymers) and their acids result ing from the hydrolysis thereof (whichhydrolysis may also give esters).

The peroxy agents (b) are used in relatively substantial proportionsrelative to the olefin (x). The previous examples show (x):(b)equivalent ratios [i.e., computed as ratios of each (x) to each OO- (b)]that are substantially 1:0.3 to substantially 1:0.15, but the actualequivalent ratios which may be used range from a practical minimumeffective amount in the neighborhood of 20:1 to 100:1

( below which no significant benefit is ordinarily obtained from the useof the peroxy agent) to a practical maximum of substantially 1:1,although perhaps 2:1 is more practical in most instances, depending oncatalyst costs since there is ordinarily not more than nominal advantageobtained in using ratios above substantially 3:1 to2;1.

A unique and significant feature of the instant invention resides in adistinction drawn between the use of inorganic H 0 (b and the organiccatalyst initiators, b which latter agents (A might be expected to havesome compatibility with the organic reactants x) and/or (a) even if theart appears to suggest undesirable reaction mechanisms, e.g., Equation(B), supra. In the instant use, however, H 0 should be expected tofunction, if at all, in any of several undesirable fashions, e.g.,Equations (B) supra and/or( G) or (H) infra. The apparently incompatibleconcentrated (aqueous) H 0 (h is added to anhydride (a), separately fromorganic (x), using reaction temperatures often above 100 C. at whichdecomposition and/or volatilization and/or some other undesirablefunction of the agent (b might be expected to occur.

In contrast it has been found that, although the H 0 (b does not givequite as good a yield herein as an equal molar proportion of organicagent (b the H 0 la) is so much less expensive than the organic agentsb) that the cost advantages far exceed the disadvantage of a loweryield, and the yield may be very inexpensively increased by using more H0 Although the present invention contemplates the use of H 0 b as anessential and predominating catalyst or initiator( b), i.e., more thansubstantially 50 mol percent and preferably to mol percent of b); theuse of the organic peroxy agents, e.g., (b in the remainder of theoverall molar proportion for b) is permitted (and even recognized asaffording advantages which compensate for the added expense of suchorganic agents, when used in comparatively smaller molar proportions).In such instances H 0 (h is still added separately, of course. Theorganic agent A (b,) is predissolved, when used, since the use oforganic peroxides and/or hydroperoxides has certain advantages in thatthese materials may be more readily dissolved in most of the anhydridereactants (a) and/or the olefin reactants (x), but the organic agentsare often quite expensive, so their use in a solution in order toincrease their convenience and effectiveness is significant.

The process of this invention may be repeated with comparable resultsusing a corresponding minute molar proportion of any of the followingorganic peroxy" free radical promoting agents (b) (in combination withmajor proportions of H (b tertiary butyl peroxide (b t-butylhydroperoxide (b benzoyl peroxide (b cumene hydroperoxide (b tetralinhydroperoxide (b diisopropyl benzene hydroperoxide h t-buty1perbenzoate(b acetyl peroxide (b urea peroxide (b methyl ethyl ketone peroxide (bdiisopropyl ether peroxide (b diisopropyl peroxy dicarbonate (b It willbe understood that some of the more readily decomposed organic peroxidessuch as (1) above function more effectively at temperatures below thespecified 135-9 C. and corresponding adjustments in the reactiontemperatures are made to achieve optimum operating conditions for thevarious organic peroxides (b and (b through (b with the major proportionof H 0 (be), which appears to function well over a substantialtemperature range.

The reaction temperatures in the case of a major reactant (a) such asacetic anhydride are preferably the reflux temperature for the aceticanhydride, at least in situations wherein the acetic anhydride iscapable of dissolving all or substantially all of the olefin (x) at suchreflux temperatures, which are substantially 134-9 C. The reactiontemperature may, however, range from a minimum effective temperaturethat may be as low as perhaps 75 to 100 C., although reactiontemperatures above 100 C. are preferred in most instances and a maximumpractical reaction temperature of about 200 C. (e.g., range ofsubstantially 105 to 205 C.) is ordinarily not excessive for goodresults in the practice of the invention. The upper reaction temperaturewill often be limited primarily (as well as easily controlled), underatmospheric pressure, by the reflux temperature of the predominatingmaterial, i.e., usually the anhydride, e.g., (a acetic, b.p. 134-9 C.;(a propionic, b.p. 168 C.; (a or (a.,) butyric or isobutyric, b.p.s.192, l82.5 C.; and (a valeric, b.p. 205 C., anhydrides. Even though (x,)camphene, b.p. 157 C. or (x beta-phellandrene, b.p. 176 C. may havelower boiling points than some anhydride reactants (a), the resultingproducts (P) will not and slow incremental additions of the olefin (x)and/or initiator (b H 0 will have only a nominal effect on the refluxcondition. Subsequent stripping of the excess anhydride (a) and/orinerts or unreacted olefin (x) may be and usually is completed atreduced pressures, and various pressures may also be used for carryingout the entire reaction within substantially the overall temperaturelimits hereinbefore indicated. The peroxide agent (b) i.e., H 0 with orwithout an organic peroxide is a material which is decomposed by heat atvarious rates depending upon the overall conditions and, of course, theactual temperature to which this agent (b) is subjected. Ordinarily, thereaction system is set up under operating conditions which will afford apreferred rate of decomposition for the catalyst (without drastic orexplosive decomposition), so that the function of the catalyst inpromoting free radical formation will take place under optimum reactionconditions for maximum yield. The cost of materials involved isordinarily such that the time of reaction is not as critical aconsideration as the overall yield of the product, and similarconsiderations of this nature; but the operating temperature employed issuch that the overall reaction time will be reduced to a practicalfigure, at least to the extent that this may be done without undulysubtracting from certain essential features such as the percent ofyield. In this respect, the subsequent Table I indicates a number. ofvariables for a given reaction system (i.e., camphene and aceticanhydride), as a guide for carrying out the specific reaction describedand/or comparable reactions using other reactants. In Table I it will beseen that the top portion thereof designates in successive columns fromleft to right the run number, the camphene purity, the mo] ratio of(a):(x), the reaction times (for addition and for overall time), and theultimate stripping temperature employed. In the lower half of Table I,designated Table IA, it will be seen that the columns, from left toright, indicate the run number, the product saponification number, andthe conversion computations which indicate the number of equivalents ofacetic anhydride reacted, the number of mols of camphene reacted, thepercent camphene reacted and the'percent of 1:1 or equi-molar adductobtained in the product. The other reaction conditions of substantiallyacetic anhydride reflux temperature, incremental addition of olefin andperoxide, etc.', specifically described in Examples 1 through 3 hereofare used in the various Runs designated on Table I, unless otherwisespecified on such Table.

The use of the foregoing acid anhydrides herein is easily demonstrated,for example, by carrying out the procedure of Example 3 hereof using theanhydrides (a) of a cut of saturated coconut oil fatty acids (a (a (a (aand (a in the relative proportions found in the coconut oil, suchanhydrides being formed initially by refluxing the acids with aceticanhydride (i.e., for about 10 hours and then stripping off the lowerboiling acetic anhydride). The resultant anhydride mixture (50equivalents) ismaintained at substantially C. during (8 hours of)incremental separate additions of camphene (x and hydrogen peroxide (hin the amounts specified in Example 3 (with the camphene predispersed inabout 390 g. of such anhydride mixture at about 50 C.). The 150 C.temperature is maintained for an additional 16 hours and then pressureis reduced to strip off the unreacted anhydride (at substantially 150C./0.05 mm. Hg.) so as to obtain the product mixture (P cg lCII-CIIzCIIR-CO dodecyl group. In each of the foregoing procedures theseparation of the excessanhydrides (a and/or (a to obtain the products(P and (P is simplified because of the absence of product mixtures, andalso higher yields are obtained (or at least are ascertainable).

The foregoing procedure may be repeated using (a nonanoic anhydride;stripping off of excess (a is effected at substantially 100 C./0.04 mm.Hg. The same conditions are used for mixtures of (a (a (0, (a and/or (aor for the individual anhydrides. In contrast, a better yield isrecoverable using individually or mixtures of anhydrides (a (a (a and/or(a and stripping off the excess anhydride at 160 C./18 mm. Hg.

In the case of (a (a and/or (a.,) the procedure of Example 3 is followedexactly (using corresponding molar proportions), including refluxingduring reaction and stripping off excess anhydride as described, thereaction temperatures being 168 C. (a 192 C. (a and l82.5 C. (a,),respectively, obtaining the corresponding anhydrides of the camphenepropionic (P -butyric (P and -isobutyric (P acid adducts.

Corresponding results are obtained by first preparing as above,anhydrides of acids (a through (a except that the anhydrides ofdicarboxylic acids, (a to (n will form the corresponding di-adducts ateach of the alpha carbon positions present in such dicarboxylic acidmolecules. Thus, the product (P obtained using one or more anhydrides(a,) through (a has the formula:

(wherein for cycloaliphatic reactants (a R R becomes a divalentpentamethylene group, but in general) wherein each R and R may be H or asaturated aliphatic hydrocarbon, i.e., alkyl, aralkyl, alkaryl,cycloaliphatic, etc., and the total number of carbon atoms in R plus Ris not more than about 16. The product (P obtained using succinic (023)or other dicarboxylic acids (a et seq. has the formula:

e 1 CO CH2 i CHCH2 I C 2 I R4 0 H2 i/C-CH3 GI 06 CH2 CH3 2 amount of theacetic anhydride, and it is found that the excess anhydride is removedto obtain the resultant adducts: camphene-succinic anhydride (Pcamphenesuccinic-adipic-anhydride mixture (P or campheneadipic anhydride(P depending upon the selection of the starting reactant (a).

As shown above, the general procedure of Example 3 is used withvariations but using 30 percent hydrogen peroxide (b as an initiator orcatalyst for the promotion of free radicals. By comparison of suchresults with Table l, tertiary butyl peroxide (b,) appears to be thebetter free radical promoting agent (b) for use in the instant reaction(A) from the point of view of reaction yield or percent conversion of(x), reaction efficiency generally and/or on the basis of minimumequivalents (or mols) of (b) per equivalent of (x). Other organic agents(b) may be used in place of (1),) to obtaincomparable excellent resultsin the previous Examples 1 and 2. The successful use of hydrogenperoxide (b however, has also been demonstrated herein, and it will beappreciated that hydrogen peroxide, as such, is readily available invarious relatively inexpensive nonaqueous (e.g., ethanol) as well asaqueous concentrations, generally ranging from about 30 percent byweight to approximately percent, or even percent by weight. The amountof water or other volatile (e.g., ethanol) actually incorporated at anytime with a given typically small incremental addition of hydrogenperoxide (according to the procedures of Example 3 and theDemonstrations hereinbefore described) is so very small, that such wateror volatile carrier will not change the substantially anhydrouscharacter of the reaction mixture. The acetic anhydride (a,) or otheracid anhydride (a) is present initially in a sufficiently great quantityso that the water will react rapidly with the anhydride to give a verylow concentration of free acetic or other organic acid and the hydrogenperoxide will carry out its function in an essentially organic medium(i.e., essentially the acid anhydride plus a very small amount of freeacid and nominal amounts of product already formed and the incrementalportion of olefin added contemporaneously with the addition of hydrogenperoxide).

The hydrogen peroxide in such essentially organic medium appears toreact such that it functions effectively for the promotion of freeradicals in the manner desired. According to Table 1, the actual yieldobtained, as the basis of percent conversion of (1 mol) of camphene (xusing (0.3 mol) hydrogen peroxide (b is substantially 60 percent of thatobtained using about one-half the molar proportion of an organicperoxide, such as (0.15 mol) tertiary butyl peroxide (b but the use ofhydrogen peroxide (b affords substantial economic advantages in spite ofthis apparent inferiority. This is so primarily because the H 0 (b inany of its conveniently available concentrated (30, 50, 70, 90 percent)forms is so much less expensive that the organic initiators (b), i.e.,peroxides, hydroperoxides, ozonides, etc. Also, the approximately 30percent lower conversion of camphene (x to the adduct (P,)

I using H 0 does not mean that the entire proportion of camphene (x,)not converted (in Ex. 3) is lost or wasted, since the same can bereprocessed with the acetic anhydride (a and without significant changein essentials of the stripping operation required to remove the excessreactant (al Not only is the price per pound of an organic peroxide suchas t-butyl peroxide (b many times higher than that of (b,) H 0 (activebasis); but 0.15 mol of organic (b weighs about twice as much as 0.3 molof (b H 0 (active). Hence, the greater molar or equivalent ratio for(b): (x) that is preferred for use of H 0 and, also, the greaterequivalent ratio for (a):(x) that is preferred for best results with H 0will both involve only nominal cost disadvantages that are faroutweighed by the expense alone of the organic initiator.

It will also be appreciated, however, that particularly in unusualsituations involving perhaps some specific operating problem and/orolefin (x):anhydride (a) reaction system, it is possible to obtainsubstantially the foregoing economic operating advantages with superiorpercent olefin conversion yields also, simply by using for a given molof olefin (x), the preferred 0.3 mol H (b plus a small amount of organicperoxide (b e.g., such as about 0.015 or 0.03 mol, which would effect anapproximate organic initiator cost saving of some 80 to 90 percent butwhich will ordinarily effect disproportionately greater increase in thepercent yield (conversion), when such is expedient or desired. Actually,up to 25 mol percent or even approaching 50 mol percent of the totalinitiator (b) could beam organic peroxy compound [dissolved in theolefin (x), etc.] for purposes of effecting improved yields; but it isbelieved that the maximum economic advantages obtained by the use, incombinatiomof organic peroxy and H 0 2 (b initiators involves theforegoing approximately minute mol percent to mol percent (i.e., 0.015to 0.03 mol) of the organic initiator (b predissolvedin the olefin (x)as shown. Without being limited to any theory, it is believed thatcontemporaneous slow incremental addition of H 0 in this instance willeffectively cooperate with rather than subtract from the betteryield-producing properties of the organic initiator, substantiallybeyond that which could be expected from the small molar percent used.

The procedures of each of the following Examples 4 through 7 may berepeated using, instead of acetic an-- hydride (a propionic anhydride (aand comparable results obtained, the reflux reaction temperature,however, being about 168 C. Repeating the same procedure using butyricanhydride, (a and/or (a one obtains comparable results using the refluxtemperature (about l82-192 C.); but somewhat better yields are obtainedif a controlled temperature for the reaction is maintained atapproximately l50-l60 C. Comparable results are obtained, however, usingvarious other anhydrides (a,,) through (a in the previous proceduresdisclosed herein, but using in place of camphene (x,), the cyclicolefins of Examples 4 and 5, namely, B-pinene (x and d-limonene (x;,),which are the olefins used in Examples 4 and'5. Comparable results arealso obtained using the organic peroxy compounds (b and (b through b,;;)in the proportions actually described in Examples 4 through 7 (in thecombinations with H 0 The use of hydrogen peroxide (b alone in Examples4 through 7 results in good yields at significant economic advantages,although numerically only about 60 percent as high yields as aredescribed in Examples 4 through 7, using organic (b alone.

Examples 1, 2 and 3 hereof can be repeated using valeric anhydride (a inplace of (a and refluxing at 205C. and the resultingalpha-(camphany1)-valeric anhydride (P is obtained.

It will thus be seen that the process of the invention is essentiallythat of producing an alpha-substituted ac)l anhydride; and in definingsuch compound herein the alpha-substituent may be identified by alphafollowed by the identification of the alpha-substituent in brackets orparenthesis, e.g., alpha-[C terpenyl substituted]-acetic anhydride, or-C to C alkanoic acid anhydride, in which latter case the anhydrides (a)are acetic to valeric, all boiling substantially within the range of to205 C. In the case of valeric anhydride (a (b.p. about, 205 C.) thereflux temperature is considered to be at the top of the practical rangeof l00-l05 up to 200-205 C. (which is a desired condition for agenerally anhydrous reaction scene), although even within this preferredrange it appears that better yields are obtained at substantially to C.,i.e., using (0 (a (a (a,,) and/or (a which does not involve refluxing atatmospheric pressure but is still a controlled reaction temperature, andone which need not be exceeding in subsequent sub-atmospheric pressurestripping. Additional embodiments of the process and products of theinvention, wherein the ingredients are designated by the previouslyidentified subscripts to (a), (x), (b), etc., include:

II. Repeating the procedure of Example 3 using (a in the same(25 mol)proportion and temperature (i.e., l35l40 C., but without refluxing), theproduct obtained in comparable yield is: (P21) alpha-(dihydrocamphenyl)-propionic anhydride. III. Repeating the foregoingprocedure (II) using 1 mol of (1: instead of (A1,), a comparable resultis achieved in obtaining (P22) Alpha-(cyclopentyl methyl)-propionicanhydride; and, likewise, (IV) with (x,) the aIpha-(cyclohexylmethyl)propionic anhydride (P is obtained;

IV. with (x methylenecycloheptane, the product (P isalpha-(cycloheptylmethyl) propionic anhydride:

V. with (x and (x respectively the exocyclic CH becomes thealpha-methylene linkage, i.e., CII between the (x and (x cycloolefinresidues and the alpha-carbon of the propionic anhydride in hydirdes ofsuch monocarboxylic acids and (x alphasubstitution is obtained in parton the foregoing 1:1 adduct basis, e.g., (Palpha-(Vinylcyclobutylethyl)- propionic anhydride or alkanoic anhydride;but the reaction tends toward an adduct of 1 mol of (x,,) per 2 molarequivalents of (a through (a e.g., (P

Generally represented:

( 311; /CH2 CH3 CHCHzCHrCH CHCHzCHz E which is theoretically comparableto and obtained in yield comparable to those of the product of Example7, which could be represented:

*S=Saturated N g H In contrast, (IX) if a dicarboxylic acid anhydride isused, in accordance with the procedures herein, but

with essentially monofunctional (x) compounds such as (x through (x (xthrough (x the results are comparable with essentially 2 mols of (x)adding to one mol of such dicarboxylic acid anhydride through (a but (X)using di-functional (x an essentially equimolar addition product of (xand (0 through (a is obtained and (XI) using tri-function (x with suchdicarboxylic acid anhydrides (a through (a (in the procedure of Example7 hereof), the product is essentially an (x): (a) adduct in 2:3 molarproportion, but in both (X) and (XI) hereof, the yields include theother possibilities, i.e., 1:1, 1:2, 2:1, etc., and this aspect ofidentification is complicated, even though it is possible to ascertainthat the dominating reaction is alpha-substitution.

In thecase of the monocyclic (C terpenes, i.e., those containing carbonatoms, the C l-l (x;,),

W (x (x (x) and (x terpenes are preferred in one category, and the C l-l(X and (x in the other. The products are respectively alpha-(C Hsubstituted)- and alpha-(C l'l substituted)- acyl compounds. Thebicyclic terpenes preferred are (x (x (x and (x which result in alpha-(Cl-I substituted)- acyl compounds. Preferably the terpenes used have areactive exocyclic methylene CH carbon which is unsubstituted (as in theso-called alphaor primary olefin); but lower C C alkyl groups on suchexocyclic C are not precluded, e.g., (x or (x Likewise, although vinylcycloaliphatic hydrocarbons (x (x (x etc., produce good results herein,it is found that particularly in the case of the various monocyclicterpenes (x (x (x as well as bicyclic terpenes (x the unsaturation maybe between two exocyclic Cs, as in the typical isopropenyl group -C(CHCH instead of a simple unsubstituted vinyl group -CH CH Althoughpreviously indicated, thecompounds of the invention can be described onthe basis of the addition products of so many (x) groups to so many (a)groups, at the alpha-position on (a); and the resulting (x) group forany given starting reactant (x) differs only in that a reactant (x)unsaturation is satisfied by one H and one bond (which, in turn,attaches to the acyl group as a replacement for the original alpha-H),it is apparent that a fundamental structure in the product is JA -iro-Wvl Ml 7| and preferably the resultant C to C hydrocarbon group (x),which contains only C and H atoms, and which has no acetylenicunsaturation and not more than one or two ethylenic unsaturation.Benzenoid unsaturation is not excluded and not considered functional orreactive herein. On the foregoing basis, of course, the reactant (x)must be represented as which is a C C cycloaliphatic olefin, differingfrom the group (x) definition only in that there is the additionunsaturation (and the alpha, beta and gamma C designations are changed).Preferred terpene reactants and groups compare, as follows:

Reaetuut (x) Group (x) mHis erppuo C H terpouyl (luoioeychc) (monocyclicsaturated) (X10) CH2 C Hr- CH(CH3)p CH(CII:)2

( 15) CHa OH:

I S C=CI{'3 S CHCII2 41H: 6H3

I C II: I g C .H:

CH CH; CHO H: C Ha CH3 i), 13) a OH:

I $=CH2 mCH-Olfi- CH3 Hg (bicyclic) J 021 s CH2 0E stomi/T C Ha 0 H3 CHa C Ha (x1e) A CHaC CH3 S+OHz CHaCCHa S+CHZ Hence preferred compoundsof the invention are alpha-[C terpenyl]-acy1 anhydride of a C to Ccarboxylic acid, viz. alpha-[C l-l terpenyl]-acetic anhydride andalpha-[C H 19 terpenyl]-acetic anhydride.

The foregoing description herein has been devoted to a substantialextent to the use of relatively higher molecular weight cycloaliphaticolefins (x,) .through (x and (x,,,) which is mentioned hereinimmediately after (x These olefins are quite often relatively expensivecompounds as such. As previously indicated herein, perhaps the mostsignificant feature of the instant invention resides in the fact that itis possible to obtain unique and unusual economic advantages by the useof inorganic hydrogen peroxide as the principal if not the only freeradical initiator used in the practice of the invention. In sodescribing this aspect of the invention, however, it has been pointedout that the significant economic advantages accompanying the use ofinorganic hydrogen peroxide result in yields which are very good, infact unusually good in view of what might be expected from theapparently incompatible inor-' ganic hydrogen peroxide used with theorganic coreactants (x) and (a). It has also been pointed out hereinthat certain aspects of the somewhat better yields that are obtainableusing the organic peroxy-type initiators (b and (b et seq. happen to beobtainable at substantially greater initiator cost, if such organicperoxy compounds are used alone, and in the total absence of theinorganic hydrogen peroxide (b2) initiator. Also, it has been pointedout that it is possible to obtain an exceptional yield advantage byusing the inorganic hydrogen peroxide (b in combinations with relativelyminor molar proportions of the organic peroxy initiators (b) (i.e., suchorganic compounds being used in very small amounts will be found toinvolve much less cost for the initiator, as compared to using organicinitiators alone, while one appears to be able to obtain acorrespondingly greater yield advantage than the use of such relativelyminute amounts of the organic initiator would suggest). In the case ofcertain of the previously mentioned olefins (x), it will be found thatat least some ,of these materials are quite expensive and aresufficiently difficult to handle so that the last-mentioned proceduremay afford, at least in some exceptional instances, economic advantagesover the use of the inorganic hydrogen peroxide initiator (b alone.

On the other hand, it will be appreciated that the practice of theinstant invention is not necessarily limited to the use of expensiveand/or potentially technologically difficult complex olefins. Instead,the instant invention affords, in perhaps a somewhat different categoryof advantage, unusual economic advantages in carrying out of thefundamental reaction hereinbefore indicated as Equation A), using manycomparatively inexpensive olefins and/or olefinic-type compounds (x)having the requisite ethylenic unsaturation for alpha-substitution onthe acyl group of the acid anhydride (a) reactants, which have beendescribed herein. In such instances, the anhydrides (a) are ordinarilynot extremely expensive and/or particularly difficult to handle in theexcess amounts required in order to obtain the advantages of the instantinvention. Also, many simple olefins such as the generally recognizedaliphatic alpha-olefins, and a number of other well known olefinicallyunsaturated olefins and nonolefins, all of which fall with the genericcategory of the compounds x) may be used in the practice of the instantinvention with unusual economic advantages, using often the inorganichydrogen peroxide initiator (b) as the sole free radical promotinginitiator (b), for the reason that it was found that the techniquesdescribed herein afiord verygood yields of these compounds and theunreacted or unconverted ethylenically unsaturated reactants x) are veryeasily reprocessed and otherwise handled so that the overall economicconsideration may often be merely the cost of the peroxy initiator (b)used in the reaction of the instant invention, involving suchlast-mentioned category of unsaturated compounds. In this respect,attention is directed to the following typical embodiments of theinvention as just mentioned. The embodiments are specificallyillustrated by Examples 8 through 1 1.

The foregoing discussion and Examples 8-1 1 demonstrate ratherconvincingly that in the case of the relatively simple alpha olefins,particularly l-dodecene (x there are distinct advantages in the use ofthe higher mol proportion of about 0.3 mol H plus the higher and/orreflux reaction temperature 135-140 C., plus slower and more gradualincremental additions of the olefin and peroxide to the refluxing aceticanhydride as well as a longer overall reaction time.

In practicing the invention using the aforesaid alpha olefins, if theboiling point of the olefin (x) is not sub- 24 described in the priorart patents using gaseous ethylene, for example, could not be used). Itwill beappreciated, however, that pressure reaction vessels will have atendency to afford some operating sophistication, in view of the factthat the gradual addition of the hydrogen peroxide quite apparentlyaffords distinct advantages andsuch would be required to add the samegradually even in the case of a pressure vessel. On the other hand,continuation of heating the reactants substantially after the additionof the hydrogen peroxide is completed in the practice of the instantinvention also affords distinct advantages herein, and this is notcomplicated in any way by the useof pressure vessels such as the typejust mentioned. The removal of the anhydride reactant (a) is againeffected ordinarily by simple distillation, but it may also be done bywashing with water, which is a procedure that may afford a number ofadvantages in instances involving more volatile reaction products (P Theremoval of the unreacted olefin is, of course, not a difiicult procedurein any case, since it will have a substantially different boiling pointfrom the reaction product in any case. In addition, it will beappreciated that the residual reaction product may be used as suchand/or converted by conventional methods to soaps, free acids, methyl,ethyl, butyl, etc., esters, known amides, nitriles, etc., allsubstantially as described hereinbefore in connection with theconversion of earlier anhydride reaction products, and also as shown inExample 10 hereof.

The embodiments of this invention will be further illustrated by but arenot intended to be limited to the following examples. Examples 1-3hereof illustrate the use of (x camphene as the olefin. A commercialgrade of camphene is used containing 83 percent actual camphene; theremainder is chiefly tricyclene, a saturated isomer of camphene which isnot understood to react with acetic anhydride (a,) under the conditionsused.

EXAMPLE I -A solution of 136 g. commercial (x camphene (1.00 mol total,0.83 mol actual camphene) and 22 g. tbutyl peroxide (0.15 mol) in 390 g.acetic anhydride ((1,) is added incrementally over a period of eighthours to 2160 g. acetic anhydride total of 25 mols or 50 equivalents)maintained at the reflux temperature (138-39C.). The reaction mixture isthen refluxed for 16 hours longer, then excess acetic anhydride, isdistilled off at atmospheric pressure until a pot temperature of C. isattained and only 304 g. of material remains. Of this remainder, 300 g.is vacuumstripped to a pot temperature of 150 C. at 6 mm. Hg pressure,leaving a residual liquid product of g. This product has asaponification number of 338.8, corresponding to 0.95 equivalent ofcombined acetic anhydride and 0.80 mol of combined camphene, or 96percent of the actual camphene charged. This product comprises mostlythe symmetrical anhydride of 3,3- dimethyl-2-norbornanepropionic acid (PCOO as shown by the acetic anhydride/camphene ratio of 1.19 and by thefact that the product when esterified with ethanol contains 82 percentof the corresponding ethyl ester (calc. S.N., 251; found 252.1, 252.4).

Further runs using camphene and acetic anhydride in the presence oftertiary butyl'catalyst are summarized in Table 1 and IA below.

REACTION OF CAMPHENE WITH ACETIC ANHYDRIDE TABLEI v Mol Reaction time,

Camphene ratio, hr. Max. purity, A020: stripping percent camphene Addn.Total temp., C.

TABLE 1A Conversion Camphene Percent 1:1 Product A020 adduet in Run NoS.N.4 equiv. mol 2 percent product 3 1 At reflux, using 0.15 molt-BllzO: per 136 g. commercial camphene, except in D where 0.3 mol ofH402 was used.

- Per 136 g. of commericai camphene charged. 3 As determined byesterification. 4 saponification number.

EXAMPLE 2 The preparation described in Example 1 is repeated except thattwice as much camphene (X and t-butyl peroxide are used, keeping theamount of acetic-anhydride (a,) the same; reaction temperature is 134139 C. and final stripping temperature is 164 C. at 12 mm. Hg. A productis obtained with saponification number of 326.0, corresponding to anacetic anhydride/camphene ratio of 1.12 equivalent per mol and aconversion of 92 percent of actual camphene charged. The butyl esters ofthe product contain 83 percent of the ester of the 1:1 adduct.

EXAMPLE 3 A solution of 136 g. commercial camphene in 390 g. aceticanhydride is added from one addition-funnel,

and 34.2 g. 30 percent hydrogen peroxide (0.3 mol) is added separatelybut simultaneously from another addition-funnel, incrementally over aperiod of 8 hours, to 2,160 g. acetic anhydride maintained at the refluxtemperature (l34-138 C.). The reaction mixture is then refluxed for 16hours longer, then the excess acetic anhydride is distilled off atatmospheric pressure until a pot temperature of 150 C. is attained andonly 290 g. of material remains. Of this remainder, 288.5 g. isvacuum-stripped to a pot temperature of 150 C. at 7.5 mm. Hg leaving aresidual liquid product of 95.5 g. This product has a saponificationnumber of 334.0, corresponding to an acetic anhydride/camphene ratio of1.16 equivalent/mol and a conversion of 59 percent of actual camphenecharged.

EXAMPLE 4 A solution of 22 g. (0.15 mol)' t-butyl peroxide 5,

in 136 g. B-pinene (x (1 mol) is added over a period of 8 hours to 2,550g. acetic anhydride (25 mols) maintained at the reflux temperature(137-139 C.). The reaction mixture is then refluxed for 16 hours longer,then the excess acetic anhydride is distilled off at atmosphericpressure until a pot temperature of 150 C. is attained and 414.5 g. ofmaterial remains. Of this remainder, 412 g. isvacuum-stripped to a pottemperature of 152 C. at 12 mm. Hg., leaving a residual liquid productof 174 g. This product has a saponification number of 320.9corresponding to 1.00 equivalent of combined acetic anhydride and 0.91mol .of combined B-pinene. In this case, a rearrangement takes place inthe cyclic olefin ring and the major ingredient of the product is thesymmetrical anhydride of 4-isopropy1- cyclohexene-l-propionic acid, (P

If the foregoing Example 4 is repeated, using as initiator (b) only 11g. of (b,) (0.075 mol), plus 34.2 g. of 30 percent H 0 (b (0.3 mol), theyield of (P,;,) is only slightly lower; and if this procedure is againrepeated using only 2.2 g. of (b ),(0.015 mol), 3 still lower yield isobtained, in which case such yield is still obtained at a significanteconomic advantage.

EXAMPLE 5 A solution of 22 g. (0.15 mol) t-butyl peroxide (b,)

in 136 g. d-limonene (x (1 mol) is added over a period of five hours to2,550 g. acetic anhydride (a maintained at the reflux temperature(136.5-l38.5 C.). The reaction mixture is refluxed for 1 hour longer andthen worked up as in the previous examples. The final strippingtemperature is C. at 12 mm. Hg. A liquid product (P is obtained withsaponification number 302.4, corresponding to 0.54 equivalent ofcombined acetic anhydride and 0.53 mol of combined limonene.

1f the (b,):(b peroxide combinations are used (according to the secondparagraph of Example 4) in procedures, otherwise repeating the foregoingExample 5 comparable results are obtained.

EXAMPLE 6 A solution of 22 g. (0.15 mol) t-butyl peroxide (b in 108 g.4-vinyl-1-cyclohexene (x (1 mol) is added over a period of 8 hours to2,550 g. acetic anhydride (a maintained at the reflux temperature(134139 C.). The reaction mixture is refluxed for 16 hours longer andthen worked up as in the previous examples. The final strippingtemperature is C. at 10 mm. Hg. A liquid product (P is obtained withsaponification number 335.4, corresponding to 0.45 equivalent ofcombined acetic-anhydride and 0.48 mol of combined vinylcyclohexene.

Again, if the (b ):(b peroxide combinations in the relative molarproportions previously specified (according to the procedures of thesecond paragraph of Example 4 hereof) are used in the procedure of the 1above paragraph of this Example, substantially the same results areobtained.

EXAMPLE 7 A solution of 22 g. (0.15 mol) t-butyl peroxide (1),) and 54g. l,2,4-trivinylcyclohexane (x (0.33 mol) in 102 g. acetic anhydride (ais added over a period of 8 hours to 2,448 g. acetic anhydride (total 25mols) maintained at reflux (l37-l 39 C.). The reaction mixture is thenrefluxed for 16 hours longer and then worked up as in the previousexamples. The final' stripping temperature is 92 C. at 13 mm. Hg. Acrumbley rubbery solid product (P is obtained with saponificationnumber. 497.4, corresponding to 0.90 equivalent of combined aceticanhydride and 0.34 mol of combined trivinylcyclohexane (i.e.,approximately 1.02 equivalent).

Again, if the (b ):(b peroxide combinations in the relative molarproportions previously specified (according to the procedures of thesecond paragraph of Example 4 hereof) are used in the procedure of the.above paragraph of this Example, substantially the same results areobtained.

EXAMPLE 8 I p To 2,5 50 g. (25 mols or 50 equivalents) of aceticanhydride (a there is added, incrementally over a period of 5 hours, 168g. (1 mol) of l-dodecene (x 0) and 34.2 g. (0.3 mol) of 30 percenthydrogen peroxide from separate addition funnels. The reaction mixture(b is maintained at the reflux temperature during this time and for 1hour thereafter. Most of the excess acetic anhydride (a is thendistilled from the reaction mixture at atmospheric pressure. Of the remaining 287.5 g. of reaction mixture, 282.0 g. is stripped under vacuum(to a pot temperature of 149 EXAMPLE 9 To 2,550 g. (25 mols) of aceticanhydride (n there is added, incrementally over a period of five hours,168 g. (1 mol) of l-dodecene (x and 34.2 g. (0.3 mol) of 3540 C. Thedried product amounts to 215.5 g. and has an acid number of 218.2.According to gas-liquid chromatographic analysis, the product containsabout 66 percent myristic acid (P EXAMPLE 10 A 100.0 g. sample of thecrude myristic anhydride (P prepared in Example 8 is refluxed with 400g. of anhydrous methanol and 4.0 g. of concentrated sulfuric acid for 2hours. About three-fourths of the methanol is then distilled off and theremainder of the methanol is washed out with water. The remainingproduct is washed with 5 percent sodium carbonate solution, dried overmagnesium sulfate, and then vacuum distilled. From 100.0 g. of driedproduct there is obtained 67.0 g. of a water-white fraction, boilingmostly at 96-99 C. at 0.3 mm., which has a saponification number of231.8 (calculated value for methyl myristate is 232).

EXAMPLE 1 l The variations in the process of Example 8 are evaluated bymaking comparisons of procedures related thereto using l-dodecene as theolefin (x). The procedures and results so obtained are tabulated inTable 2 (below):

N.B.-Conditions other than stated in the table are the same as given inExample 8.

It will be appreciated that the foregoing Examples 8- through 11, andparticularly the comparative results shown on Table 2 above, suggestpreferred techniques 30 percent hydrogen peroxide (b from separateaddition funnels. The reaction mixture is maintained at the refluxtemperature during this time and forl hour thereafter. Most of theexcess acetic anhydride is then distilled from the reaction mixture atatmospheric pressure, then the pressure is reduced to 10 mm. of mercuryand distillation is continued until only 218.0 G. remain in the reactionflask. This remainder is then saponified by adding 1,600 g. of 5 percentsodium hydroxide solution and stirring at 95-99 C. until a clearsolution is obtained 1 hour). The clear soap solution is then dilutedwith 4,400 g. of warm water and allowed to cool to room temperature. Theslurry of precipitated sodium salts is then acidified with a solution of220 g. of concentrated hydrochloric acid in 660 g. of water and theresulting product is filtered off,

washed with water, and dried in a vacuum oven at and/or operatingconditions for the use of hydrogen peroxide as the free radicalpromoting initiator (b which is used alone in this particular group ofexamples for the purpose of demonstrating preferred operating proceduresfor the use thereof. On Table 2, Runs D1 and El suggest that the lowermol proportion of 0.15 mol, plus the lower operating temperature of -80C. and a relatively short addition time will result in a product (Pwherein the equivalents of the olefin, ldodecene (x for each equivalentof acetic anhydride (a are almost two to'one, which might be desirablefor some purposes in connection with the telomer type of formation, butwhich is not specifically preferred as a result in the practice of theinstant invention. Instead, the results on Table 2 tend to point outsubstantially how one may obtain very good yields with the alpha olefinl-dodecene (x using hydrogen peroxide (b in the procedure of theinvention. It is thus apparent that Run E1 of Table 2 shows that apreferred result, over that of Run D1, is obtained by increasing theoperating temperature to l35-140 C. (i.e., the reflux temperature of theacetic anhydride used), plus the use of a slightly longer reaction time.It will be seen that the product (P obtained in Run E1 of Table 2 muchmore closely approaches the preferred 1:1 (equivalent 3,689,537 -2 ml v30 ratio) adduct which is desired in the practice of the inexcellentyield results in unusual economic advantages vention. It will further benoted that, at least in the case in the practice of the invention. Also,the use of an acid of the alpha olefin l-dodecene (x the higher molar asthe unsaturated reactant (x) is demonstrated, but

proportion of 0.3 mol H plus the use of reflux ternusing the anhydrousco-reactant (a in excess, as peratures for the excess acetic anhydridereaction mix 5 Stated foredefinitely is to be preferred for purposes ofobtaining th re pect to the foregoing comparison between the product (Pand( It, with the latter indicating a organic (b,) and inorganic" H 0 (bcomparative superior overall yield and a better yield of 1:1 adduct, yies forgiv n reactants n under given 9 .1

apparently as a result of the much slower rate of increditions do oftenshow better yields as such at least for mental addition of the reactants(i.e., 8 hours as compreferred organic promoters, such as tert.-butylperoxpared to 5 hours, plus atotal overall reaction time of 24 'ide([2,) but the extreme savings in cost of materials hours as compared toonly 6 hours for Run Al using H 0 (b much more than compensates forthis.

Other more specific examples showing variations in x) and( a) includethe following: 1 5 EXAMPLE .13

EXAMPLE 12 The procedure of Example 8 is repeated using as (x) thevarious alpha-oletins and blends thereof recited on To 2,550 g. (25mols) of acetic anhydride a are Table 3A and 3B below, and comparing 30%B 0, (b added, over'a period-of 5 hours, 184 g. 1 mol) of 10- withtert.-butyl peroxide I4 in various proportions undecenoic acid (r and34.2 g. (0.3 mol) of 30 perzo and for somewhat different reaction times.Unless cent hydrogen peroxide (b from separate addition specified inTables 3A-B below the conditions proporfunnels, while maintaining thereaction mixture at the tions and ingredients used in each run are thoserecited reflux temperature. After additional refluxing for 2 in previousExample 8. hours, the excess acetic anhydride is distilled off, first "Wat atmospheric pressure, then at 1 8 mm. (to a pot tem- TABLE peratureof 153 C.). The semi-gelatinous product (233 i (1. i -gigflgi s rgu a ce a i gg g.), comprising poly(brassylic anhydride), is esterified withmethanol to give 17 g. of methyl lO-undecenoate I Initiator v and 104 g.of dimethyl brassylate. Olefin used m m To 2,550 g. (25 mols) of aceticanhydride (a,) is added, over a period of 8 hours, a solution of 8 2-{f:.:::::::::::::::::::::::: $9.20. 9'1? 2 5 mol) of lO-undecenoic acid(x and 22 g. 0.15 mol) 3 3g: K3328: g g of di-t-butyl peroxide (b whilemaintaining the reac- I gt 51 3 1 202 .0; g 2% tion mixture at thereflux temperature (l37- C.). C Cwa-01efinb1end: 'I H202 is a a After 16hours of additional refluxing (l357 C.), the '*%g*j-' f}f j}? :1 E28: f;5 g reaction-mixture is worked up as described in Example 01 gg-,; -,;g-,g II 565 :2 g g 12. The semi-gelatinous anhydride product amounted fig a lgfin blend gig; g g to 247 g., which is esterified to give 6 g. ofmethyl 10- 2 2 undecenoate and 1 14 g. of dimethyl brassylate. TABLE 3BIt will be seen that the initial anhydride product in this Example 12 isactually a polymeric anhydride, 33, 33,333- percent formed according tothe equation sequence (N) below: Olefin used m lg gggggg M v e??? i3;CH2=QH(OH2)3COOH [CHz=CH(CH2)sCO]gO 83.: :3? l A020 4 CrCr a-olefinblend. 81 C6-C1!) a-olefin blend. 87 Co-Cw a-olefin b1end .90 0 Do .91[AcOi JCHQOHNHA Da l c.. f;ai;a1;r1t;a::

Ora-C11 a-olefin blenrL. l-octadecene Examples 14 and 15, below, providea specific com- 5 l i if] parison between acetic (a) and the next higherT Aczo "propionic (a and butyric (a anhydride showing a rombmssyncanhydride) distinct difference; but also showing unusually good resultsusing such higher anhydride (a and (a Also, these Examples 14 and 15show that the preferred or- Using either hydrogen peroxide (b-,) ort-butylperox- 6Q ganic promoter (a obtains correspondingly lower ide (bessentially the same polyanhydride was ob yields which againdemonstrates how the economics of tained which was readily converted tothe mon mer c the invention can be judged or predicted quiteinteldimethyl brassylate. ligently based essentially upon thecomparisons demon- The somewhat better yield obtained using the stratedherein relative to the use of H 0 plus whatever ganic peroxide (1);) l5not insignificant from the point Of knowledge the skilled worker mayacquire from this View Of yield alone; but the fact that the much lessspecification (or otherwise) with respect to the use of pensive and morereadily available H 0 (b gives an tert.-butyl peroxide (b EXAMPLE 14 To2,925 g. (22.5 mols) of propionic anhydride are; added over a period of5 hours, 151 g. 0.9 mol) of 1-; dodecene and 30.6 .g. (0.27 mol) of 30percent hydrogen peroxide from separate addition funnels. A reactiontemperature of 138140 C. is maintained during the addition and, for 1hour thereafter. Most of the excess propionic anhydride is removed byvacuum distillation, leaving 171 g. of product with a saponificationnumber of 281.6, corresponding to 0.76 mol of dodecene and 0.95equivalent of propionic anhydride per mol of dodecene charged. Thisproduct is mostly amethylmyristic anhydride, as shown by esterifyingthe, product with methanol to give a mixture of esters con-; taining 82percent methyl a-methylmyristate.

EXAMPLE 15 To 2,760 g. (17.5 mols) of isobutyric anhydride are added,over a period of five hours, 1 17.6 g. (0.7 mol of l-dodecene and 23.7g. (0.21 mol) of 30% H from separate addition funnels. A reactiontemperature. of 150l5 1 C. is maintained during the addition and for onehour thereafter. The reaction mixture is worked up as in Example 14,giving 33.7 g. of anhydride: product corresponding to 0.16 mol ofdodecene and 0.28 equivalent of isobutyric anhydride per mol of dodecenecharged. When the reaction is repeated using: 15.4 g. (0.15 mol) of t-BuO dissolved in the dodecene, instead of the H 0 added separately, and areaction temperature of 15l-l58 C., the anhydride product amounts to53.4 g. and corresponds to 0.28 mol of dodecene and 0.38 equivalent ofisobutyric anhydride per mol of dodecene charged; the methyl esters madefrom this product contain approximately 75 percent methyl,a,a-dimethylmyristate.

In spite of certain correlations between (b and (b which have beenexplained herein, it must beappreciated that such correlations applyonly to the extent taught herein. Thus-prior art workers may and dosuggest the use of certain agents to promote various reactions betweenolefinically unsaturated compounds such as (x) hereof and variousgeneral classes of com-. pounds containing an acyl group (with orwithout an available alpha-hydrogen). It must be appreciated that suchlatter acyl compounds, if outside the scope here disclosed and claimedare essentially non-functional. with H 0 (b even though they mayfunction with (b,). Examples 16, 17 and 18 show such comparisons, below:

EXAMPLE 16 To 885 g. (15 mols) of acetamide is added, over a Pld of12%?! ss gtip f 9.4. 2- m of dodecene and 6.6 g. (0.045 mol) of t-Bu O Areaction temperature of 137-139 C. is maintained during the addition andfor 1 hour thereafter. The reaction mixture is then cooled to about 85C. and the excess acetamide removed by washing with water. There isobtained 48 g. of a solid product containing 4.12 percent nitrogen,corresponding to 0.78 mol of dodecene and 0.48 mol of acetamide per molof dodecene charged. When the reaction is repeated using 10.2 g. (0.09)of 30% 11,0, (added separately) instead of t-Bu 0 a liquid product 146.7g.) containingonly 0.035 percent nitrogen is obtained-corresponding toonly 0.0037 mol of acetamide per mol of dodecene charged.

EXWPFE 7...

To 2,700 g. (45 mols) of glacial acetic acid is added over a period offive hours, a solution of 168 g. (1 mol) of l-dodecene and 22 g. (0.15mol) of t-Bu,0 in 300 g.

5 l f t' Te e'c' 'ureis ainiairi e 2i l effifi?( f1 tiring t z ad diiionand for 2 hours thereafter. Most of the acetic acid is then distilledoff at atmospheric pressure and the remainder EXAMPLE 1 8 To 3,000 g.(50 mols) of glacial acetic acid are added, over a period of 5 hours,168 g. (1 mol) of 1- dodecene and 134.2 g. (0.3 mol) of 30% H 0 fromseparate addition funnels. The reaction mixture is held at the refluxtemperature during the addition and for 2 hours thereafter, and is thenworked up as in Example 17. The residual product amounts to 121 g. andhas an .acid number of 5.9, a saponification number of 227.6,

and a hydroxyl number of 54.0; corresponding to 0.54"

mol of combined dodecene, 0.013 equivalent of acid, and 0.48 equivalentof ester. Dilution of the recovered acetic acid distillate with waterliberates 70 g. (0.42

mol) of unreacted dodecene.

The embodiments of the invention in vwhich an exclusive property orprivilege is claimed are defined as follows:

1. 3,3-dimethyl-2-norbornane propionic acid.

